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CHAPTER I
INTRODUCTION\
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Quantitative organic and inorganic estimations involve the ability to
design reagents such as polymers, crown ethers, cryptands, calixarenes etc.
which can target a desired ion and provide quantitatively efficient
selectivity and isolating that ion from its surrounding environment. Organic
means of
reagents with increased selectivity, sensitivity and specificity towards
inorganic ions have found utility in diversified fields like agriculture,
pharmaceuticals, biochemical, environmental studies, chemical analysis etc,
Presently, a large number of organic reagents1'6 targeting inorganic analysis
are known.
Calixarenes, of vase like macrocycles, have been under
development in the research laboratories for the last 50 years. The origin of
calixarenes was put in the form of phenol-formaldehyde chemistry in the
laboratories of Baeyer in 1870’s.7 He obtained uncharacterizable resinous
tars as a condensation product of phenol and formaldehyde in’pfresence of
mineral acid. Blumer,8 Storey9 and Luft10 tried to tame these tars and were
unable to produce materials with marketable quality. Success was to go to
Baekeland11 when he filed a patent in 1907 on his process to make
Ba kdlite.12
13-14Zinke and co-workers were among the first to carry out a
systematic investigation of the phenol-formaldehyde reactions. They
simplified the problem by looking at p-substituted phenols instead of phenols1A.
to avoid cross-linking problems. Zinke proposed a cyclic tetrameric
structure for his base catalysed reaction product in accordance with Niederl
and Vogel15 who had also proposed a cyclic structure to compounds,4'
obtained by acid catalysed treatment of aldehydes and phenols. The
pioneering efforts of Zinke and his co-workers introduced to the chemical
world a series of compounds whose structures appeared to be accurately
and adequately described as the cyclic tetramers.14 The other method,
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Hayes and Hunter synthesis16 provides a classic example of the use of a
halogen as blocking group.16 This method demonstrated its potential in the
preparation of a series of tetramers, pentamers, hexamers and heptamers.
Few years later this method of synthesis was further exploited and
Later Cornforth20 ventured into the Zinke17-19improved by Kammerer et al.
procedure and contradicted Zinke’s assumption that a single product is
formed in every instance. Under similar reaction conditions he isolated
higher melting and lower melting materials from p-tert-butyl phenol and
p-octyl phenol. Cornforth inferred that both compounds are diastereo
isomers arising from hindered rotation. However, Kammerer et al.
Munch21 contradicted this assumption with 1H NMR data. Munch et a!.
investigated the petrolite dftnulsifier made by oxyalkylating the condensation
product of j>-tert-butyl phenol and- formaldehyde and concluded that although
the recipe was different from the one described by Zinke, the material that*
they had isolated must be a Zinke’s cyclic tetramer.
17,18 and
22,23
24-26Gutsche, the pioneer of Calixarene chemistry, has chosen Zinke’s
product as a potential candidate for enzyme mimic building. He coined the
name “calixarenes" for these products. The name is derived from the Greek
‘calix’ mean vase and ‘arene’ which indicates the presence of aryl residues '
in the macrocyclic array. He further used different substituted phenols and
elucidated the condensation products as cyclic tetramers.24 Gutsche
demonstrated that the outcome of the reactions can be strongly influenced
by reaction conditions, thereby showing the synthesis of various calixarenes.
All structures were in complete agreement with chemical, spectral and*
analytical data, moreover, definitely established by single crystal X-ray
crystallography by Andreetti, Ungaro and Pochini.27'AWider community of
researchers have been carrying out several attempts to exploit this new
area.
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Several methods are in practice for designing the calixarenes with
functional groups. It involves:
reactions at lower rim
reactions at upper rim
oxidation reaction of calixarenes
(a)
(b)
(c)
Due to their molecular architecture, easily manipulate cavity
dimensions and application in recognition of organic molecules and metal
ions, they have been recently named as third generation molecular
receptors. This new class of macrocycles $
applications in different fields. With the horizon of complexation abilities and
salient properties of calixarenes increasing, there is an increase in the
finding extensive
number of reports, monographs and patents. Most of the patents feature
calixarenes as an item of commerce.30 However, most of the recent
applications are associated with their properties as molecular receptors.31
Calixarenes can be widely used as collecting agent for cesium from nuclear
waste,31 as extractant of uranium from sea water,31 chromatographic
column,32 ion-selective electrode,33
exchanger39 etc.
34-38metal complexing agents, on-
The scientific challenge today lies in combining this useful
understanding and rich information with a reasonably vigorous theory so that
the reagent selection and design can be put onto a more scientific footing. A
scientific approach to reagent design for selective separation involveÿ two
important surface chemical aspects, namely (a) the selectivity of the
appropriate functional group which provides interaction specificity to the
reagent and (b) design of the corresponding molecular architecture
depending on its end use.
40-49The use of organic reagents in mineral processing
inevitable due to their efficiency in achieving selectivity in the inorganic
has become
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separations. The mineral processing industry over the past few decades had
to evolve appropriate means to treat difficult to process ore deposits. The
development of highly selective mineral processing reagents, which are not
merely metal ion specific but specific to the particular mineral structure, is
essential for the exploitation of relatively more difficult to process ore
deposits. In view of the rapidly increasing demand of metals and materials
and fortunately also for a developing country like India, it is essential to have
a comprehensive strategy for * optimum utilization of national mineral
resources, while short term ad-hoc measures become necessary from time
to time in response to change in the international market situation, we
should also have a long term strategy to exploit our limited natural resources,
so as to build a self-reliant economy to the maximum extent possible. This
long term strategy would include the development of appropriate technology
to process the low grade complex ore deposits available in the country.
50,51 also called as China clay, is amongst the most widespread
materials on the earth’s surface. The mineral kaolinite, chief constituent of
Kaolin,
kaolin, is one of the commonest and versatile minerals found in the
uppermost 10 meters of the continental crust, ranking in abundance along
with minerals viz., quartz, mica, feldspar and calcite. Kaolin is the
mineralogies! name for a white hydrated aluminium silicate mineral.
Structurally, kaolinite consists of alumina octahedral sheets and silica
tetrahedral sheets stacked alternately51 and has the theoretical formula
<OH)8Si4A!4O10.
Kaolins are classed as primary and secondary deposits50. Primary
kaolins are those formed by alteration of crystalline rocks such as granite
and remain in the place where they were formed. However, secondary
deposits of kaolin are sedimentary and have been transported from their
place of origin and deposited in beds or lenses associated with other
sedimentary rocks such as sands.
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Kaolin reserves are spread over all the parts of the world. Most of the
reserves are associated with impurities viz., unkaolinised feldspar, Fe, Mg,
Ti, Ca, K and sodium oxides, mica, tourmaline etc., which may be inherent in
the parent rocks. The presence of silica and feldspar in the finest size
constitute the grit material50 which renders it unsuitable for its use in the
manufacture of high-class products. The presence of iron and titanium oxide
minerals are disadvantageous as they impair whiteness and reduce
brightness, an important property for industrial utility. The other impurities
which have less impact on clay system are tourmaline and mica.
The commercialization of the crude kaolins woufd require the
elimination of the high profile discolouring impurities viz., anatase Ti02 and
Fe203 in the clay matrix. Research reveals that anatase Ti02 is one of the
Although commercial,51,52major discolouring impurities in the kaolins.
synthetic and pigment anatase is pure white with a brightness close to 100,
the anatase occuring in kaolin is dark reddish brown coloured, probably due
to iron substitution within its lattice. In addition to anatase Ti02, there is also
the presence of rutile Ti02 which occurs mostly in coarser particles. Since, in
the normal wet processing of kaolin, the extreme coarse particle fraction is
discarded. Rutile Ti02 is removed along with the coarse particle fraction
hence it is insignificant discolouring impurity.
Upgraded kaolins by minimising or eliminating these impurities have
splendid industrial applications viz., ceramic, paper, rubber, paint, textile,
plastic and pharmaceutical industries and new utilities are still being
discovered. The prime importance of kaolins lies in its chemical inertness,
whiteness, hiding power as an extender, reinforcing characteristics, low
conductivity of heat and electricity etc.
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Some impurities are separated through particle size separation and
some through simple water washings. Other methods carried out involve
removal of the major discolouring impurities in the clay matrix viz., anatase
Ii02 and hematite.
Some important upgradation techniques of the kaolin are discussed below:
China Clay
Dry processing Wet processing
CalcinationAir flotation
Gravity separationChemical bleaching
Magnetic separationFroth flotation
Selective flocculationBiobeneficiation
DryProcessing:
The essential feature of Dry process53(a) involves the drying of the
crude kaolin followed by pulverization.
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AirFlotation
Mb removes most of the grit and coarse
kaolin particles as underflow. The air flotation is relatively simple, has lower
costs, lower yields and lower quality products which are used as low-cost
filler ii the rubber, plastic and paper industries. The process involves the
following three steps:
The Air Halation process
Crude clay is shrudded into small pieces of size less than 1 inch.
Drying of the shrudded pieces by rotatory drier.
Further pulverization of the crushed clay in air-swept roller mill.
Wef Processing:
Wet processing11, a more elaborate processing scheme which resuits
in products of improved uniformity and brightness. It is by use of specialized
techniques within the water washing process so that increase in brightness
and colour improvement may be made. The important implications that
involve are as follows:
Preparation of kaolin slurries with water.
Removing coarse mineral impurities and undispersed clay by
screening.
Selection of the appropriate separation technique depending on the
various particle size fractions.
The various separation techniques are:
Calcination:(i)54 a is a well established age old process to produce
special grade kaolins depending upon calcination temperatures in the range
650-700°C, The process aimed at the removal of structural hydroxy groups
produces a bulky product with enhanced resiliency and opacity which are
desirable, attributed for paper coating applications.
Calcination
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Various kaolins upgraded using this technique are discussed in Tab!e-8.
(ii) Gravity Separation:
The principle of Grawfy separation
two thousand years and it remained the dominant mineral separation
technique til! the advent of advanced techniques. Gravity separation can be
successfully implemented to the ores having large differences in specific
gravity between the minerals and gangue matrix.
54(b) has been known for well over
Upgradation of kaolins through gravity separation devices viz.,
Hydrocyclones, Dorr Bowl classifier, Continuous centrifuge etc., are well
established for years being together. The most popular countries in the
international market for the supply of quality china clay viz., the UK (Cornwall
& Devon Clays), the USA (Georgia Clay deposits) and Czechoslovakia take
recourse of hydrocyclone for degritting. Gravity separation technique is not
suitable for the clays with the particle size finer than 50 microns.
Beneficiation of kaolins using this technique are discussed in Tabie-1.
Chemical Bleaching:
Bleaching56 is essentially a whitening or decolourising technique by
employing oxidising, reducing or combination of both reagents depending
upon the nature of colour imparting minerals present in the clay. Chemical
bleaching is most effective for marginal improvement in the brightness of
kaolin clays to make them suitable for paper and textile industry by way of
removal of iron bearing particles which have escaped the earlier stages of
beneficiations. The process involves the following steps:
(iii)
i) Treatment of the clay slurry (10-15% solid) with suitable chemicals to
make soluble salts of iron,
ii) Washing of the treated clay to remove excess of chemicals,
iii) Filter processing and drying of the beneficiated clay slurry.
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Table -1Gravity Separation of Kaolin
StudyS.No Technique ApplicationRequirements Ref.Other Details
1 New technique in kaolin
beneficiation
Hydrocyclones 81Hydrocyclones made of
polyurethane was described.
Compared with those of steel or
porcelain.
CD
Hydrocyclone batteriesManufacture of new
grade of high-quality
enriched kaolin
Hydrocyclones Obtained kaolin had a decreased
content of iron-contg. mineral.
2 Porcelain & 82
domestic needs
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• The chemical treatment of kaolin clays to improve brightness is mainlyi
associated with reducing agent such as sodium or zinc dithionite and
oxidizing agent such as ozone or sodium hypochlorite.
Various bleaching/leaching combinations for the upgradation of
kaolins are discussed in Tables-2-3.
Magnetic Separation:
Magnetic separation53W'5/Kb>'57 js achieved by passing the suspensions
or dry powders through a non-homogeneous magnetic field which leads to a
preferential retention or deflection of the magnetizable particulates. In
addition to applied magnetic force, separation depends on gravitational,
hydrodynamic, inertial and centrifugal forces. A review for the magnetic
separation of kaolins is summarised in Table-4.
The major discolouring impurities in the kaolin clay matrix viz.,
anatase Ti02, rutile Ti02 and hematite are only feebly magnetic with
susceptibilities typically 1CT6 cm'3. These impurities are removed, by iron-clad
solenoid High-Gradient Magnetic Separators (HGMS). The process for the
separation of discolouring impurities from the clays through magnetic
process was first patented by fennicelli in 196558 and its first commercial unit
was installed in 1973 at Freeport Kaolin’s Gordon operation by Pacific
Electric Motor (PEM) Company. Since then, the HGMS technique has gained
acceptance throughout the clay industry and has made it possible to process
lower grade crudes. Its first commercial application was improvement of the
brightness of kaolin clays, used extensively in paper, pharmaceutical and
other industries.59,60
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Table - 2
Bleaching Techniques of Kaolin
Application RefOther DetailsRequirementsTechniqueStudyS.No
Ceramics 83Na-dithionite
Chelating agent
Improvement of kaolin
brightness
Bleaching1
Hypochlorite added before
ozonation.
Phosphate before and after
hypochlorite addition
840.25-5 lb inorganic
condensed phosphate from
Na-hexametaphosphate, Na~
tripolyphosphate and
Na4P207/ton clay,
0.25 - 10 lb sodium
hypochlorite/ton clay.
Effective amount of ozone.
Reductive
bleaching.
Magn.
purification
Improvement of kaolin
brightness
2
Bleaching Oxalic acid
Fermented medium from
Aspergillus niger cultivation
as the leaching agent
Improvement of kaolin
brightness (removal of
iron impurities)
3 Paper coating
and filler
85
Processing of kaolin Bleaching (using
statistical
methods of
experimental
design)
Oxalic acid Temperature, concentration of
organic acids, Mineral concentration,
Mixing conditions, Concentration of
HaSO,
4 86
Asboric acid
Sulfuric acid
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Iron removal from kaolin Bleaching
process (factorial
experiments)
87Iron removal of 98% by treating clay
at 90° in 100 min with 1M H2S04,
4 g/L sucrose hydrolysed and at
200 rpm
5 1M H2S04> Sucrose
hydrolysed, 200 rpm stirrer
Continuous process of
kaolin clay
996 Bleaching Unbleached kaolin was bleached in a
30 wt% dispersion having pH 7.8,
using 1 lb Iron-powder/ton &
16 lb S02/ton to obtain kaolin having.
brightness 88.0
Iron- powder, S02
roNaHS04l S02 gas, Iron
powder
Bleaching using iron-powder and
S02 gas cost in lower than the
conventional bleaching process
Processing of kaolin Reductive
bleaching
897
Treatment at 120° for 30 min of a
kaolin suspension (300 g/L) in 2.5M
H2S04 contg. 1 g saccharose gave a
filtrate contg. Fe*z £ 2425 & Fe*3 65
vs Fe+3 2459 for 2M H2S04 alone.
Acid solution (low sugar
cone.), Sugar contg. wastes,
Spent milk whey, Molasses
etc. 2.5M H2S04 contg. 1 g
saccharose.
Removal of iron from
industrial minerals
Bleaching 908
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91The degritted aq. suspension (-325
mesh fraction) was fractionated to
produce a finer fraction having
particles < 2 pm, acidified to pH <5.0
to produce an acid flocculated
suspension which is treated with a
bleaching agent to reduce Fe+3 to
Fe+2 and Fe+Z is chelated by adding
chelating agent.
BleachingPurification of kaolin
clays
Bleaching agent
Chelating agent
9
92Na-dithonitew Brightness improvement
of kaolins
Chemical
bleaching
10
93Iron-powder, SOz into a mixer purging the dispersion
with S02, withdrawing an aq.
suspension of bieached material and
separating the bleached material
from the suspension. The particles of
iron may be added before or after the
addition of S02.
BleachingRemoval of particulate
minerals
11
Na-dithioniteBleachingUpgradation of kaolins Ceramics and12 94
paper
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95Bleaching Kaolin suspensions obtained after
treatment with H3P04 or its salts or
Na4P207 at 0.05 - 5 wt% showed
increase in whiteness
Whitening of kaolin
suspensions
H3P04 or its salts, Na4P20713
96Upgradation of kaolins Bleaching Paper, rubber
and ceramics
Treated aq. suspensions of the raw
materials, with gaseous Cl or Cl
formed in situ, at pH < 5.
14 Aq. suspension of raw
materials, Gaseous Cl.
Iron removal from kaolin Bleaching15 Oxalic acid, Na2S. Bleached with a bleaching liq. com¬
prising oxalic acid 0.5 - 2.5, network¬
ing agent 0.005 - 0.1, and dispersing
agent 0.001 - 0.1% at water, kaolin
5:1 - 6:1 and pH 1-6 for 6-9h.
Iron content decreases
1.34-0.64 wt% (as Fe203)
Whiteness increases 59.8 - 86.0
97
-&ÿ
Oxidation
bleaching
Removal of FeS2 and
organic impurities
Bleached by oxidation at pH 5-6 to
increase the whiteness
16 98
Na2S204l Oxalic acidBleachingBrightness improvement
of kaolin clay
17 Paper 99
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Aq. suspensions of kaolin contg. iron
and sulfur was prepd. by addn. of
waterglass bleached with
Na-dithionite, filtered and calcined at
750° for 40 min to obtain a product
contg. Fe203 1.16, S2* 0.03 & S032'0.90%
18 Removal of iron and Bleaching
Calcination
Water glass, Na-dithionite 100
sulfur contaminants from
kaolin clay
Activation, reduction and
complexation of iron ions
from kaolin
Bleaching19 Neutralisation of kaolin suspensions
were discussed
Paper 101
cnAI2(S204)3 or Zn2(S204)3 prepd. in
situ by reacting S02 or SOz-N2 mixts.
with Al or Al-alloys or mixt. of Al with
other metals. Grain size used is
100-400 mesh and the amount used
was 0.5 - 25 Kg additive/ton kaolin.
Addnl. HCI or Cr or H2S04 contg.
0.5-100% NaCI or other sol. and in
sol. Cr may be added. S02, Na2S03.
Na2S205. or their mixts. may also be
added.
Bleaching AI2(S204)3 or Zn2(S204)3Upgradation of kaolin 10220
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21 Upgradation of kaolin Chemical
bleaching
NazS204 Kaolin suspensions were treated with
NaÿO,* at room temperature,
pH 2-4.5, cone. 25-30%
Paper coating 103
22 Beneficiation of ferro-
ginous sulfur-bearing
kaolin
Bleaching Na2Si03 Fe203 reduced from 2.75 - 0.83% 104
Na2S204 Whiteness increased to 48.3 - 80,6%
23 Upgradation of kaolin Bleaching Na2HP04
H2SiF6
1 Kg kaolin in 1 Kg water bleached at
50° for 1 h, 17.5 g aq. soin. of
420 g/L Na2HP04 and 5 g/L H2SiF6.Brightness increased from 70-73.2%
105
03Upgrdation of kaolin with
the direct production of a
reducing agent in the
process
Bleaching NaHS03l H2S04 or H3P04lZn-granules
24 Zn-granules cover the bottom of the
vibro reactor
106
Bleaching Na2S204 (5-7 Kg/ton clay),
AINH4 (S04)2, Suspension
cone. 250 g/L.
Duration of the treatment is
40 - 60 min at 50 - 60°
Whitening of kaolin 10725
50% NaOH 1%, Water glass
1%, Perabotates (or) Peroxy
(2%), carbonates
Bleaching The percentages of the reagents
were based on kaolin
Upgradation of kaolin Paper mills 10826
BleachingUpgradation of kaolin 10927
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110 |Stirring 1 Kg kaolin at 50° for 1 h in
1 Kg HzO contg. 1.775 g mixt. of
80% H3PO4 and 50% AcOH
Stirring 1 Kg kaolin in 1 Kg water
contg. 8.5 g mix. of CaC03 50,
85% H3P04 115.26, 3% H2SiFe 1.5
and HzO 179.218 parts
Paper millsH3PO3, H3PO4, HCO2H,
ACOH
28 BleachingElimination of iron
contamination from
kaolin clays
Paper mills 111Upgradation of kaolin Bleaching MH2B04, M = Na,NH4 (or)
M (H2P04)2, M = Ca, Mg, Sr
Or Ba
H2SiF6, CaC03, H3P04
29
Kaolin samples reacted with
(ij CO and Cl at 550°, (ii) Cl + 10%
AICI3 at 700°, (iii) HCI at 680° to
study chlorination
Production of 112Removal of iron from
clay
Bleaching CO & Cl, A(Cla, HCI30
AI2O3 & AICI3
Upgradation of kaolin Bleaching Paper31 113
Bleaching H2S, H2SO4 H2S gas was passed through the
kaolin slurry in H2S04 at pH 2-4
(room temp.). Wahsed kaolin
samples repeatedly for 37 times
(The process resulted 76% of iron
impurities)
Separation of iron
impurities from kaolin
32 114
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33 Upgradation of kaolin Kaolin was dispersed in aq. soln.
contg. Na-poiyphosphate. Acidified
the resultant with H2S04, then
treated with NaHS03. Finally treated
with aq. urea at 30-80°. Whiteness of
the product increased
Bleaching Na-polyphosphate, H2S04
NaHS03, Urea
115
Process involved acidification, S20/‘treatment, neutralization, oxidative
treatment with Cl or H202. Then
washed kaolin suspension was
adjusted to pH 2.5 with H3P04. 0.35
Kg Na2S204/100 Kg clay were added
and stirred at 22° for 45 min.
Neutralised with NaOH to pH 8.
Treated with 9 Kg NaOCI for 10 min.
34 Upgradation of kaolin Bleaching Cl or H202, H3P04i Na2S204,
NaOCI.
116
oo
Bleaching Alkali metal chloride orRemoval of iron contg.
minerals from kaolin
Process was carried out at
850 -1100°C
35 117
Chlorate
Bleaching Urea (0.036-0.048%),
Ammonium oxalate (0.057-
0.071%), Hydroxyl amine
hydrochloride(0.243-0.321%)
HCI (0.126-0.140%)
Solution for removing
iron-containing impurities
from kaolin
36 118
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Thiourea dioxide (pH 2-8) Aq. kaolin suspension of particle size 119BleachingUpgradation of kaolin37
<1p
120The iron in a highly crystalline kaolin
is removed by fusion with (NH4)2S04.
Iron is removed by being complexed
with H2C204 (or) Na-polyphosphate
Na2S204, (NH4)2S04, H2C204or Na-polyphosphate
Bleaching38 Physico-chemical
methods of purification
of kaolins and their
mineral composition and
origin (removal of iron)
121Kaolin suspensions were treated with
1-20% (NH4)2S04. Heated at 200-
400°C. Finally treated with glass
sand and 5% H2S04.
(NH4)2S04l 5% H2S04Bleaching39 Simultaneous separation
of titanium and iron
compounds
co
Na2S20, H2S04pH 1.75-2.2
122Removal of Fe203 from
kaolins
Bleaching40
H3P04, Na2S204Production of upgraded
kaolin
Bleaching41 Paper 123
Whitening of kaolin Bleaching Na2S204, Sol. phosphate 10-20% kaolin suspensions were
acidified to pH 2-2.5 with 8-10
Kg/sol. phosphate/ton kaolin
42 124
JtJpgradation of kaolins Bleaching Aq. HN03t 0.4% KCI03 1 Kg kaolin suspensions bleached
with 5% HN03 contg. 0.8% KCIOawas boiled for 30 min with stirring
(at 293-383 K),
43 Ceramics 125
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Ceramics 126Raw kaolin was mixed with 1.5%
sulfur powder, heated in a wet Cl2
gas atm. at 110-120°.
59.7% aq. suspension (viscosity
5200 P) of clay bleached by NazS204
Cl2 gas
Sulfur powder
BleachingPilot-plant investigation
on the upgradation of
kaolin
44
127Na2S204BleachingTreatment of clay
minerals
45
128Kaolin was suspended for 10 min in
boiling soln. of oxalic acid or an
acidic soln. of a metal oxalate. Iron-
oxalate is filtered, washed and dried
which is treated with H2S to ppt. iron.
Iron sulfide ppt. is treated with H2S04to generate H2S.
Oxalic acid, H2SBleachingMineral treatment
process (removal of
iror> contaminants)
46
roo
Removal of coarse
fractions from kaolin
Bleaching47 Paper and
ceramics
129
Upgradation of kaolin Bleaching48 Na2S204l NH2OH Kaolin bleached with Na2S204followed by leaching with NH2OH at
pH < 4.5
130
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Table - 3
Leaching of Kaolin
Ref.ApplicationOther DetailsRequirementsTechniqueStudyS.No
131Cone. HCILeachingStudies on reaction1
model of kaolin
132Basic industrial
applications
Oxalic acid is capable of dissolving
all the teachable iron in kaolin
Organic acids, Citric,
Gluconic and Alkalic acid
LeachingRemoval of iron
impurities
2
133Adopting various operating
parameters such as leaching time,
temp, and reagent cone. Removal of
80% and 100% iron with ascorbic
and oxalic acid resply. Products of
whiteness 92-94% were obtained.
Ascorbic acid, Oxalic acid,
H2SO4
LeachingRemoval of iron from3
kaolin
AES, XRD and ESR analysis 134LeachingRemoval of nonstructural
iron from kaolinite group
minerals
4
Sulfuric acid treatment for aq. solns.
of kaolin.
H2SO4 135LeachingMinimisation of iron5
content
HCI, Acetone or Ethylene
glycol.
The purification time is shortened
when the aq. soln. contains HCI
3.2 - 13.6 wt% and acetone or
ethylene glycol 5.0 - 50.0 wt%
LeachingRemoval of iron-contain¬
ing minerals from kaolin
1366
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PaperpH of the system was less than 7. 137Anionic phosphateLeaching -oxidation
High solids processing of
kaolinitic clays
7
Acids, formic acids soly. For
minerals contg. esp. lion carbonates
as discolouring agents, allowing the
mineral to stand in air in a layer
<20 cm thick for 5-7 days increases
whiteness by an avg. of 2%
138Acids (Formic acid)LeachingTreating minerals
especially kaolin, for
increased whiteness
(removal of iron
carbonate impurities)
8
Temp (50-90°), Time (30-360 min)
Particle size (0.1 - 2.5 mm) H2S04cone, (25 - 200 g/L), Liquid-solid ratio
(1.5-10)
139H2SO49 Removal of iron and rare
earth elements from
ferroginous kaoiinite
Leaching
K>
Kinetic model for
upgradation of kaoiinite
Leaching HCI10 140
Beneficiatjon of kaolin Leaching HCf or H2S0411 141
Effect of forms of
occurence on removal of
iron compounds
(siderogel) from
sedimentary kaolin
Leaching HC) Calcined kaolin at 550°C for 2h
followed by leaching with 9% HCI
soln. at 100° for 1h removed 71% of
the iron.
12 142
LeachingCharacterization and
upgradation of kaolin
HCI13 DTA, IR and TGA studies 143
1 (30)
144Leaching HCISome aspects of upgra-
dation study of kaolinite
clay
14
145Separation of basic
components of kaolin
ore by acid
Leaching15
Calcination at 580° produced
92-99% Al203
146Extraction of Al203 from
clays
Leaching
Calcination
HCI16
147HCIAlumina - mini plant
operations
Leaching17
roHCI, H2S04 148Extraction of alumina
from clay
Leaching18CO
Na2S204 soln.
Na-dithionite
Removal of iron(lll)
oxide from kaolin
3 Stage
concurrent
leaching
19 Paper 149
Leaching Na2S204Multiple phase process
for removing Fe203 from
kaolin
3 Step procedure: 0.2-0.3 wt%
Na2S204 based on kaolin added at
each stage
150
1 (31)
Table - 4
Magnetic Separation of Kaolin
Other Details ApplicationS.No Study Technique Requirements Ref.
pH 5.5 -6.5Na - pyrophosphate (0.7%)
as dispersant and Natural
magnet or artificial ferrite as
magnetic seed
1 Refinement of kaolinite
(removal of iron and
titanium contaminants)
Magn. seeding 151
2 Purification of kaolin clay HGMS Superconducting
machine of 5.0T
152Magn. sepn.
HGMS Applied magnetic
field of 1.5 to 2.0T
Brightness increased upto 88.5% Paper coating3 Brightening of kaolin clay Magn. sepn. 153
Removal of iron
impurities
Super conductor magnetsMagn. sepn.4 154!\;
Wet screening
Chemical
bleaching
HGMS Superconductor
magnet, CDB (Citrate-
Dithionite-Bicarbonate)
method
X-ray, Chemical analysis and
Brightness studies
Elimination of iron
containing minerals
5 Paper coating &
filling, paints,
fine tableware
and electronic
155
fields
HGMS. Separator
(ZMG-125)
A HGMS with good combination of
vibration and pulsed motion was
designed and manufactured
Removal of iron from
kaolin clay
Magn. sepn.6 High quality
china clay
156
HGMSMagn. sepn.Removal of iron from
hard pulverised kaolin
Fe203 content reduced from
2.20 - 0.082%
7 157
1 (32)
Treating clay with a strong mineral
acid, e.g. H3P04 preferably in combi¬
nation with magn. sepn.
G.E. brightness level was increased
Paper 158HGMS, H3P04, Magn. fieldRemoval of chlorite and
siderite mineral iron
impurities from kaolin
Magn. sepn8
A new apparatus used in grading
and dressing was designed and
made for kaolin. Whiteness further
increased using a reducing-complex-
ing method
1599 Processing of kaolin Mag. sepn.
Reducing
complexing
method
HGMS
Paper 160Metal belt type HGMS,
Magnetic intensity
17,000 Oe, Belt width
600 mm, capacity 10-15 tons
minerals per hour
Recovery of hematite Magn. sepn.10NScn
r/jf «, vi Nnlet*
f HGMS, Na-tripoly phosphateRefinement of kaolin
(removal of Fe203 &
Ti02)
Beneficiation of kaolin
(removal of colouring
oxides)
Magn. sepn. 16111#*
VrV
HGMS, Na3P04l Waterglass,
Superconducting magnet
Magn. sepn. 16212
\
1 (33)
163Paper and rajor
coating
Treated by 2-stage hydraulic rotary
sand removal and gravity sepn. to
obtain products contg. 85% particles
of 2 pm diameter. After HGM
dressing and chem. bleaching to
remove Fe & Ti impurities
HGMSGravity sepn.
Magn. sepn.
Bleaching
Experimental research
on beneficiation of kaolin
13
Process resulted 70% reduction in
pyrite content and increase in
brightness of the kaolin samples
16414 Purification of kaolin
(removal of pyrite
impurities)
Magn. sepn. HGMS, Superconducting
magnets
Improvement in % brightness is
more in alkaline pH
16515 Effect of pH on
beneficiation of kaolin
(removal of iron minerals
and ferroginous anatase)
Magn. sepn. HGMS
ro05
Removal of Fe203 &
anatase impurities from
kaolin clay and study of
dispersion, coagulation
properties
16 Magn. sepn. HGMS Most desirable dispersion condn.
was at 0.1wt% of a dispersant, and
coagulating condition at 1 wt% in a
20 wt% sofid-contg, dispersion. At
the matrix loading of 0.1 in HGMS
treatment, the contents of Fe203 &
anatase were decreased from
0.97 to 0.44 & 1.05 to 0.48% resply.
Purification yield is high at avg. grain
size (£ 3pm) compared to s 11 pm.
166
1 (34)
The addition of 50 g colloidal magne¬
tite in kerosine/tcn in magn. sepn,
improves the quality of nonmagnetic
product. Its yield was 84% and the
Fe203 & Ti02 contents were 0.76 &
0.31% from the feed contg. 1.02 &
0.47% resp., & its yield was 78.3%
Fe203 content was decreased to
0.34% - 0.27%, brightness increased
from 82.16% to 87.00%
167Colloidal magnetite in
kerosine
Magn. sepn.Removal of iron and
titanium impurities
17
16818 Parameters and
methods of increasing
the brightness of kaolin
(removal of Fe203)
Magn. sepn. HGMS
N3vi
HGMS Superconducting
magnet
Discussions include superconducting
magnet design, power supply,
refrigerator cycle & reliability
169Purification of kaolin Magn. sepn.19
HGMS, OGMS Magn. sepn. of the kaolin clay with
the aid of a matrix and magn. sepn.
of electrostaticaliy collected brown
coal flue ash without a matrix are
objects of lab work in high magn.
fields. The clay was separated on
Cr steel matrix
Beneficiation of kaolin Magn. sepn. 17020
1 (35)
21 Improvement and control
of the quality of kaolin
(removal of iron &
titanium impurities)
Magn. sepn. HGMS Porcelain 171
manufacture
22 Weakly magnetic
mineral beneficiation
Magn. sepn. PEM-type HGMS Effect of dispersing agent 172
23 Removal of iron and
titanium impurities from
kaolin
Magn. sepn. HGMS Product of brightness >80% were
obtained
Paper fillers 173
hooo 24 Improvement of quality
of kaolin
Magn. sepn.
Chemical
HGMS Products of brightness >84% were
obtained
Paper industry 174
bleaching
Mineralogical properties
of kaolin and removal of
Magn. sepn. HGMS25 175
iron and titanium
Purification of kaolins by
removing iron and
titanium impurities
Magn. sepn. HGMS Purification of kaolin improved the
whiteness of the material by ~3%. A
dispersion pretreatment is required
due to fineness
26 176
1 (36)
Purification of kaolin27 Magn. sepn. Superconducting HGMS The sepn. chamber diam. and length
were 80 and 400 mm, resply. Magnet
was wound with Nb-Ti
superconducting composite (diam.
0.75 & 0.5 mm) Magnet can operate
at 5T
177
28 New role of machinery in
the industrial beneficia-
tion of kaolin
Magn. sepn. Superconducting magnets CeramicsFour superconducting magnetic
separators comprising 3 com.
systems capable of generating 2, 5
and 6T resp. and a 9T lab-system
for beneficiation of kaolin
178
roCD
Optimization of raw
material preparation
(removal of iron &
titanium impurities)
Magn. sepn. HGMS29 Paper and
Ceramics
179
HGMSMagn. sepn.Separation of iron
contents from kaolin clay
Effect of pulp density, flow velocity
and matrix type were studied. Iron
content decreased upto 0.6 wt%.
Yield of the product -60 wt%.
30 180
HGMSMagn. sepn.Purification of kaolin clay
(removal of pyrite and
anatase)
31 Porcelain 181
1 (37)
Mineralogical properties
and purification of kaolin
clay (removal of pyrite
and anatase impurities)
Magn. sepn.32 HGMS Porcelain 182
33 Removal of coloured
impurities
Magn. sepn. HGMS 183
34 Purification of clay ore Magn. sepn.
Flot. Elutriation
HGMS Produced high grade kaolins 184
35 Removal of Fe203 from
kaolin clay
Magn. sepn.
Calcination
HGMS Best results obtained by using a
matrix of galvanized steel chips,
Fe203 reduced from 1.36 - 1.09%.
After calcination at 1350°, the
whiteness is similar to that of kaolin
which does not require magn. sepn.
185
coo
HGMS with solenoid &
cryogenic installation
Purification of kaolin
clays
Magn. sepn.36 186
HGMSMagn. sepn.Effect of dispersing
agents in the cleaning
process of some clay
raw material
Ceramics, paper
and refractories
37 187
HGMSMagn. sepn.Removal of
Lepidochrocite and
pyrite impurities
18838
1 (38)
fig Magnetic field of 73000 Oe is applied
to pulp cone. 25% in presence of
flow rate of 0.64 cm/sec with
Na-hexametaphosphate. Then
bleached with Na-hydrosulfite and
H2S04 at 30-40°
189Magn. sepn.
Chem. bleaching
Upgradation of kaolins HGMS, Na-hexameta-
phosphate, Na-hydrosulfite,
H2S04
190Optimum time of the sepn. cycle was
3-4 min.
Pulp feeding velocity
0.05 - 0.33 cm/sec
HGMS of strength 1.8-2.0T
Na(P03)e (10% soln.)
Purification of kaolin
(removal of iron and
titanium contaminants)
Magn, sepn.40
co
191HGMSMagn. sepn.Paramagnetic
separation in ultrafine
industrial minerals
41
Magn. drum filters Filtered through a magn. drum filter
with permanent magnets to give
<0.1T magnetic field intensity
192Decolourisation and
purification of kaolin
Magn. sepn.42
193Magn. sepn.Separation of magneti¬
zable particles from a
fluid, (removal of
coloured paramagnetic
particles)
43
1 (39)
Magn, sepn. CeramicsFormation of aggresive substances
in kaolins and technological
possibilities of their diminution
(removal of Fe203 & Ti02)
HGMS44 194
45 Possibilities of influencing the grain
size distribution
(removal of Fe203 & Ti02)
Magn. sepn. 195
Removal of iron bearing mineral
impurities
46 Ceramics 196Magn. sepn. HGMS(2T)
47 New developments in the high
extraction of kaolin clay
20-30% solids of kaolin are mixed
with 0.2% Na4P207 in a magnetic
separator operating at 20Kg in a
consister containing steel wool.
Magn. sepn. Magnetic filters 197
Na4P207
K>
Beneficiation of kaolin (reduction of
iron and titanium contents)
Magn. sepn. HGMS48 Ceramics and 198
Paper
HGMSBeneficiation of kaolin Magn. sepn. Recovery 83-90%49 199
Magn. sepn. HGMSBeneficiation of low grade ores50 200
Removal of iron and titanium contg.
illites as colouring impurities
Magn. sepn. HGMS Applied 20,000 G magnetic field for51 Ceramics 201
30s
Magnetic separator
~15K field
Magn. sepn.
Froth flot.
The products of brightness 89.6
were resulted
Improving day brightness52 202
Jones separatorRemoval of Fe203 and Ti02 from
kaolin
Magn. sepn. The magnetic susceptibility was
(1.40- 1.63) x 10"8
53 203
1 (40)
Removal of iron contaminants from
the clay
Magn. sepn. Non-magnetic
consister contg. a
porous ferromagne¬
tic matrix
54 204
55 Removal of weakly magnetic
impurities
Aq. suspension (30% clay) was
mixed with an aq. suspension of
Fe(lll) & Fe(ll) by dissolving 12.8 g
FeCI2. 4HzO and 18.6 g FeCI3 in
200 ml HzO followed by the addn. of
61.2 ml 28% NH4OH relative amt. of
iron suspension added was
100 ml/1.81 Kg clay. This
corresponds to 3.76 Kg Fe304/ton
clay. This suspension forced through
seel-wool matrix in a magn. field of
15 Kg. After floe, the residual iron
was removed by leaching
Magn. sepn.
Floe.
Leaching
205
coCO
206Poly gradient
Magn. sepn.
(Magn. flot.
and floe.)
Magn. filtration
Beneficiation of slurries of weakly
magnetic minerals by magnetic
filtration (removal of Fe203 and TiOz
from kaolin)
56
2071000 gal of kaolin slurry/min. for a
throughput of 65 tons dry kaolin/h
passed through the magn. filters
PaperRemoval of weakly magnetic
minerals
57
1 (41)
iv) Froth Flotation:
I'he Froth flotation process54(b),55
for the recovery of valuable minerals
(10-100 microns) from ores represents the oldest and the largest practical
adsorptive bubble separation process. Froth flotation is a unit operation
which is used to separate one kind of particulate from another through their
selective attachment to air bubbles in an aqueous suspension.
The carrier flotation (piggy-back flotation or ultraflotation*
technique designed to float fine anatase particles from
clay using a conventional flotation cell. In this technique, preconditioned '
carrier particles that are in the optimum size range (e.g. -325 mesh calcite)
are added, in presence of the collectors such as fatty acids, to the flotation
circuit so that they can piggy-back micron sized anatase particles and float at
a reasonable rate. The major advantage of this process is due to the
improved flotation kinetics which in turn results in improved brightness of the
processed clay with higher recovery.
51.53(b)process) is a
Later Cundy (1969)62 developed a flotation process which requires no
carrier minerals. According to Cundy, the process cleans the minerals from
their contaminants. The essential’features of this process are two-fold.
Stage I; The scrubbing of the pulp in the presence of a dispersant and
pH regulating agent.
Stage 2: Addition of small amount of activator along with
collector.
a fatty acid-type
The collector coated impure particles may be selectively coagulated
under the condition of high-shear agitation which effectively increases the
particle size and allows them to be floated. This phenomenon is akin to the
34
1 (42)
shear flocculation (1975)63. Later Young et al. (1985)64 have developed a
flotation process which is designed to process a clay at high pulp density.
Various froth flotation reagent combinations for the beneficiation of kaolins
are tabulated (Table-5).
v) Selective Flocculation:
Although various flotation (beneficiation) processes have been
successfully employed in removing titaniferous impurities from clays, they
have had only limited success with some clays. However there have been
several Selective coagulation/flocculation processes
the late sixties and J.M. Huber corporation has been producing 90+ high¬
brightness clays from East Georgia crude kaolins since the early seventies.
51.65,66 developed since
Selective flocculation technology, a recent development in mineral
processing industry is ideally suited for separation in subsieve size range
(<10p). It involves the aggregation of finely divided particles suspended in
liquid (usually water) through the utilization of a bonding agent (polymericiii
flocculant) that ties the particles together. Particles bonded in this way form
aggregates (floes) of such large size that they can settle out of the
suspending liquid more rapidly.
Polymeric flocculants67,68 are generally those macromolecular organic
substances that cause finely divided particles to aggregate and form discrete
floes.
The essential features of the process are:
=> Grinding of the clay lumps into fine particle fractions.
=> Preparation of clay slurries with water.
Selection of the appropriate flocculants, dispersants, pH modifying
agents etc. depending on the response of the desired portions .of the
clay matrix.
35
1 (43)
Optimization of the flocculation conditions.
Filtration, drying and analysis of the recovered mineral values.
The selective flocculation technique in the beneficiation of kaolin was
in the later sixties. Due to efforts of
71-76
69.70 ;initiated by Maynard et al.
various scientists, the new technique has gained momentum in 1970’s,
Maynard (1974)'1 reports a process in which kaolinite is flocculated with a
high molecular weight and strongly anionic polymer, while leaving the
titanium and iron contaminants in suspension. Beneficiation of kaolins
through selective flocculation technique has definitely solved the purpose
upto large extent,
Literature reveals the involvement of this technique in the beneficiation of
kaolin (Table-6).
vi) Bio-Beneficiation:
Biological methods of mineral beneficiation have not even been well
understood. As different from Bioleaching, Biobeneflciation7ÿ73 by definition it
refers to removal of undesirable mineral components from an ore through
interaction with microorganisms which bring about their selective dissolution
(and removal) and thereby enriching the desirable mineral constituents in the
solid ore matrix. Earlier laboratory investigations have shown that bacteria
and fungi could be effectively used to remove iron from days.
Heterotrophic microorganisms like Aspergillus niger produce organic
acid like citric acid and oxalic acid30 during its metabolism. These organic
acids would work as chelating agents in capturing metal ions such as iron
from kaolins.
36
1 (44)
Upgradation of kaolins using this recent technique has definitely
shown some promise in mineral processing (Table-7).
The various synergic beneficiation techniques have been summarised
in Table-8.4
+
%
37*
/
1 (45)
Table - 5
Froth Flotation Beneficiation Technique for Kaolin
S.No Ref.ApplicationTechnique Other DetailsStudy Requirements
208Presence of an activator or raising
the conditioning temp, to -40° can
reduce further the Ti02 content.
(whiteness improvement: 56-79)
Paper coating
and ceramics
Processing of ultrafine
kaolin
Froth flot. Na-silicate, Oleic acid.1
209Flotation in which a blend of fatty
acid compd. and a hydroxamate
compd. was used as flotation
collector
Fatty acid, G.f., R(CO)OM,
R=alkyl, aryl or alkyloxy having
0ÿ26, and M is H, alkali metal or
alkaline earth metal.
Hydroxamate compound has G.f.
R’(CO)N (OM1)H where R1 is
alkyl, aryl or alkoxy having
and M1 is H, alkali metal or
alkaline earth metal
Removal of impurities Froth flot.2
coco
Particle size distribution s.t. £ 85 wt%
of the particle <2 pm ESD (equiv.
spherical diam.) Product of G.E.
brightness 89 to 91 was obtained.
Froth flot.Preparation of refine
kaolin clay (coarse and
fine and blended coarse
and fine)
Paper 2103
1 (46)
The addition of aq. ammonia and
ammonium sulfate buffer solution
helps the adsorption of oleic acid
211Oleic acid, Neutral oil,
aq. Ammonia,
Ammonium sulfate
Dual-liquidRemoval of iron from4
flot.fine kaolin
212Fe203 removal >98% and kaolin
recovery >90%
Dual-liquidRemoval of iron from
kaolin
5
flot
213First froth flot. rejecting the float
cone, contg. at least a portion of the
Si02 impurities, subjecting float tails
to a second froth flot., removing the
2nd float cone, as a kaolin-bearing
stream, removing the paramagnetic
particles from stream through
HGMS. Rejecting > 2 pm particle,
leaching 2 pm stream to dissolve
Fe+2 recovering kaolin.
HGMSFroth flot.
Magn. Sepn.
Removal of Si02, quartz,
feldspar, ilmenite and
other impurities
6
coCD
1 (47)
Subjecting a slurry of the crude
mineral mixture to flot. in the
presence of a sufficient amount of an
alkalimetal or NH4 afuminate compd.
to improve the removal of the
impurities (Na-aluminate in amts, of
0.5 wt . parts/ton and oleic acid as
collector) resulting kaolin brightness
84.7%, yellow index 7.8, Ti02 0.85%,
Fe203 0.41 wt% against 80.7, 10.1,
1.81 and 0.45 resply. for the
unfloated control.
214Alkali metal (or)
NH4 aluminate (Na-aluminate)
Oleic acid.
Froth flot.Removal of titaniferous
and iron oxide impurities
from crude kaolin clay
7
Sample was wet ground, water was
added to make 15% slurry. Add
H2S04 to pH 3 Na-silicate 2 Kg/ton
was added as quartz dispersant,
slurry conditioned for 5 min, flotation
was carried out for 10 min. The resp.
kaolin grade and recovery for this
process were 68.3 & 32.2% vs 68.0
& 24.5% when lauryl amine acetate
was used as collector
215Separation of kaolin
minerals
Froth flot. 2-ethyl hexyloxypropylamine,
H2S04, Na-silicate,
Polypropylene glycol,
Laurylamine.
8o
Calcite (<44p) as carrier,
Na-oleate (4 Kg/ton) as collector
Carrier flot.Removal of iron
impurities from kaolinite
Iron-reduced from 2.5 - 1%9 216
1 (48)
217Analysis was carried out using video
fluorometry
A qualitative determina¬
tion of residual flotation
oils on beneficiated
kaolin clays
Flot.10
218Study is related to DLVO (Derjagin,
Landanu, Verweg, Overbeek)
Calcite, Oleate solns.A theoretical approach
for beneficiation of clay
(removal of anatase)
Carrier flot.11
4ÿ
Flot.
Polygradient
Magn. sepn.
Extraction of contami¬
nating impurities from
kaolins, (removal of
Fe203 and Ti02).
21912
1 (49)
Table - 6
Selective Flocculation Separation of Kaolin
Ref. |ApplicationOther DetailsS.No Study Technique Requirements
Paper coatingClay product of superior brightness
was obtained
2201 Beneficiation of kaolin Synergic
phenomena
(Selec. Floe, and
Ozonisation)
discolored kaolin
Paper coating 221Ti02 reduced from 4 to 0.6%
Brightness improved from
80.0-90.4%
Recovery 73%
Purification of kaolin
(removal of coloured
titaniferous pigment)
2 Selec. floe. Anionic polymer,
Polyacrylate salt (dispersant)
Oleic acid, Polyvalent cation
CaCI2ANJ
Dispersed aq. pulp was
preconditioned for selec. floe, with
anionic polymer by addition of a fatty
acid (oleic acid) & sources of
polyvalent cation (CaCI2)
222Anionic polymer,
Polyacrylate (dispersant)
Oleic acid, Polyvalent cation
CaCI2.
Separation of mixture of
finely divided mineral
particles (removal of
coloured titaniferous
impurities)
Selec. floe.3
Na-hexametaphosphate
Polyacryl amide
Pyrophosphate, Water glass
Selec. disp. floe. 223Beneficiation of kaolin4
1 (50)
Selec. dispersing a slurry of kaolin
by the addn. of water glass, Na-
hexametaphosphate, Na-poly-
phosphate, Na-humate and polyacryl
amide
224Selec. disp. floe. Na-hexametaphosphate
2400g/ton,
Water glass 3000 g/ton,
Na-polyphosphate
2400 g/ton,
Na-humate 1000 g/ton,
Polyacrylamide 1.0-2,0 g/ton
Removal of iron from
kaolin
5
225Removal of iron from
kaolin
Shear floe. Na-oleate6
226Separation of gangue
minerals from kaolin day
matrix
Selec, disp. floe,7
to
The sludge contg. (0.1 - 1.5) x 10ÿ g
solids/L with 80-98% particles of
0.1 - 125 pm diam. is mixed with an
anionic or cationic polymer (avg. mol.
mass 5x103 - 7x106 g/mol) at 5x10‘3 -5x102g/Kg. Then the flocculated
sediment contg. (3.5 - 5) x 102 g
solids/L is homogenised and the
thickened sludge is mixed again with
an anionic or cationic polymer at
(2-4 10'1 g/Kg)
Anionic or cationic polymer8 Separation of non-poiar
and slightly polar
particles
2-Stage floe. 227
1 (51)
Paper coating 228Optimum amts, of selec. flocculants
were added to a kaolin ore slurry
Selec. floe.Separation of fine
impurities
9
229PorcelainRecovery ratios of floe, and magn.
sepn, were 49.9 and 79.98% resply.
Treatment of kaolin
(reducing Fe203 content)
Magn. sepn.
Selec. floe.
10
Paper coating 230Na-hexametaphosphate,
Na-metasilicate,
NH4CIO.I - 1.0 Ib/ton clay
Water drspersable anionic
polymer 0.01 - 5.0 Ib/ton
day, Na2S204;
NatCO 8872 (flocculant)
Beneficiation of kaolin Selec. floe.11
Ceramics, food
and paper
231Trisodium polyphosphate
(dispersant), NaOH,
Superfloe 214 (flocculant),
H2S04
The slurries at pH 12.3 were stirred
for 15 min at 600 rpm. Then stirring
was continued for 1 min by adding
0.04% superfloc. 214. Adjusted to
pH 7-11 (to flocculate muscovite) to
pH 6-7 to flocculate quartz.
pH 3.8-5.95 to separate kaolin.
Separation of quartz,
muscovite and org.
impurities from kaolin
Selec. floe.£ 12
Hydrolysed PAM Sedimentation depends on the
nature of localised adsorption
centers on the dispersed phase
Floe.Effect of chemical
inhomogeneity on the
rate of kaolin
sedimentation
13 232
1 (52)
Adsorption of polymer to Floe.
sodium kaolinite
14 PAM H-bonding between amide and
hydroxyl groups. Free hydroxyl
groups acting as adsorbing sites on
both sides. pH controls the extent of
polymer adsorption
233
Separation of alunite
from kaolin
15 Selec. floe. 234Waterglass, PAM 4% Kaolin suspensions were
dispersed with water glass followed
by PAM floe.
16 Beneficiation of low- Seq. disp.
Selec. floe.
235
grade kaolinsAUl Beneficiation of minerals Selec. floe.17 Anionic polyelectrolytes,
Na-polyacrylates, Na-
silicate, Hydrolysed PAM
Deflocculated suspensions (16.6%)
treated with an anionic polyeiectro-
lyte and then stirred with Na-poly¬
acrylates and 0.07% Na-silicate.
Then adjusted to pH 9.5 with NaOH.
Contents were mixed with 100 ppm
(based on crude kaolin) and 40%
hydrolysed PAM (avg. m.w. 3x106).
Then suspension was fed at
10 L/min into the top of a square
tower to get 87.1% products
236
1 (53)
i i'i . .. „ " -ninr « = »' *ÿ 1
-JI-»-
Na2C03, (NaPCÿ)*, Anionic
PAM
Selec. floe.
Magn. sepn.
Deflocculated with 0.1% (NaP03)*,
0.05% Na2C03 and steving to
remove particles >25 mesh. Resul¬
tant suspension adjusted to
pH 6.5-7.5 and passed through
HGMS. The treated suspension
further deflocculated by addn. of a
0.5 wt% mix. of 50/50 (NaP03)x and
Na4P207 at pH 6.5 - 9.5. Finally
selectively flocculated by the addition
of high m.w. anionic PAM.
Beneficiation of kaolin
(removal of impurities)
Paper16 237
Clay beneficiation
(discolouring crude
kaolins)
05 19 Na6PfjO-rg, Na2C03, Na2S204,
PAM, H202l H2S04i Na2S204
Magn. sepn.
Selec. floe.
Impure kaolin deflocculated using
2 lb Na6P6018 and 1 lb Na2C03/tonore, blunged to 40% solids, degritted
to remove particles >325 mesh.
Centrifugation, suspension with 5 lb
Na4P207 and 5 lb Na6P6018/ton and
ground 4 min at 600 rpm. HGMS for
2 min. The floes were blunged 30 s,
heated to 60°, treated with 0,5 gal
H2Oz/ton, flocculated with 10%
aq. H2S04 to pH 3.0, leached with
Na2b204.
Paper 238
1 (54)
239 II20 Berteficiation of kaolin
(removal of halloysite)
Selec. floe. Refractory
materialFroth flot.
21 Enrichment of kaolin
quality by fractional
separation
Selec. floe. Na-siiicate, H2S04 High quality
porcelain
240
J-J
1 (55)
Table - 7
Bio-Beneficiation of Kaolin
Ref.ApplicationTechnique Other DetailsStudyS.No Requirements
241Whiteness: 63.20 - 79.64Removal of iron
impurities from kaolinite
Bio-beneficiation Microorganisms
Bacillus SP. IRB-Wand
1
Pseudomonas SP.IRB-Y.
Sugars {1-5% wt/wt; Sugar/
clay) Glucose, maltose and
sucrose
OO
Aspergillus niger, (citric,
oxalic and asboric acid)
Best results were obtained with
mixture of citric and oxalic acids and
at a ratio of 2:1 and temperature of
90°. Iron removal was 37% and 40%
Bio-beneficiation 242Removal of iron from
kaolin and quartz
2
1 (56)
GlassChemical, mineralogicaf and particle
size analysis of kaolin sample.
Selection and isolation of suitable
microorganisms able to solubilize
iron.
Preparation of microbially produced
organic acids.
Leaching the samples with chem.
derived organic acids and with a
fermented medium produced from
desulfurised beet molasses.
Biological treatment of effluents.
243Bio-beneficiation
Leaching
Removal of iron from
industrial minerals
Microorganisms
Organic acids
3
manufacture
CD
Iron reduction by using microbial
mixed cultures was obtained (£ 81%)
while significant iron reduction in the
presence of single microbial cultures
was achieved (£37%). Finally
molasses as C source for
heterotrophic bacteria were
successfully tested
244Genera Bacillus
Agro bacter
Bio-beneficiationRemoval of iron from
kaolin ores
4
1 (57)
Purification and recovery
of industrial minerals
(removal of pyrite
impurities)
2455 Bio-beneficiation Microorganisms
6 Removal of limonite,
geothite, hematite from
kaolin
Bio-benefication Aspergillus nigerÿMolasses
Treated with cultivation of the fungus
Aspergillus niger at 30° in a nutrient
medium containing molasses as a
source of C and energy.
246
cno Treatment of mine.al raw
materials with micro¬
organisms (removal of
iron)
Bio-beneficiation Strains of T-ferrooxidans, T-
thiooxidans
247
Upgradation of kaolin8 Bio-beneficiation Silicate bacteria of strain
4(T-2) at 28±1°Faience and
refractory uses
248
1 (58)
Table - 8
Other Beneficiation Techniques
Ref.ApplicationTechniqueS.No Study Other DetailsRequirements
Enhancing the whiteness
of calcined kaolin
Paper filler and1 Additive method Chlorite or Oxides 249
ceramics
Purification of kaolin2 250Al203/Si02 weight ratio 0.42
Iron removal from
kaolinite
3 Chloridizing
roasting
Rising rate of temp., fixed roasting
temp., time, atmosphere in the
furnace
Tubing furnace 251
4 Beneficiation of kaolin Gravity sepn.
Pulp screening,
Froth ftot.,
Bleaching
252
tn
Whitening of contamina¬
ted kaolin (removal of
iron and titanium
contaminants)
5 Degritting
Delaminatiion
20-70% slurry, Aq. acid
solution
Degritting the slurry, delaminating
the degritted slurry, fractionating the
degritted slurry, subjecting slurry to
magnetic field, reductiveiy leaching
the slurry, contacting the slurry with
an aq. acid solution to convert the
chlorite/biotite micas into kaolin with
a dissolved metal salts
253
Centrifuge
fractionation
Magn. sepn.
Reduction
leaching
1 (59)
Leaching with oxalic acid in an
autoclave of 1 h at 120° and
pressure of 5-6 bar gives 90%
decreases to the initial content. Iron
oxalates converted as iron
hydroxides and oxalic acid was
recycled
254Oxalic acidHydrometallurgi-
cal process
Reduction of iron content6
of kaolin
255Production scale, products structure
and utilization of tailings were
discussed
Processing of kaolin7
Paper coatings,
ceramics, rubber
and plastics
256400 g kaolin & 500 g 0.75% aq.
polyacrylate dispersion was mixed
with 0.05% Na-dodecyl sulfate &
0.1% complex (I) solution. Products
resulted the increase in whiteness
upto 88%
Aq. polyacrylate, Na-dodecyl
sulfate, Pthalocyanine-metal
complexes(l)
Brightness improvement
of kaolin
8CDW
Calcination at temp. 100-1600°CCalcinationUpgradation of kaolin9 257
Calcination
Gravity sepn.
Magn. sepn.
Froth flat
Bleaching
Beneficiation of barite
and kaolin
10 258
1 (60)
Processing of kaolin Centrifugal (or)
Precipitation
methods
11 Nylon (or) Corundum balls Scraper coatings 259
12 Upgradation of kaolin Delamination Delaminated in a wet grinder,
defined to a level of 30, 35 & 40% by
centrifuging in a disk nozzle
centrifuge
Paper coating 260
13 Enrichment of china clay
raw material
Material enriching
method
Kaolin raw material in 5-20 Kg
portions in a container mixed for
1.5-2 h with water & NH3 at
400-600 L/ton raw materials and
1.8-2.0 L/400-600L water resply. The
resulting slurry was passed through
vibrating sieves (0.15 - 0.5 and
0.075 - 0.12 mm) which are set an
angle 3-8° and wetted with water
spray at various rate. Resulting
suspension is dehydrated, formed as
14-15 mm strips and dried to 15%
moisture content.
NH3, Vibrating sieves 261
uico
Centrifugal sepn.Beneficiation of kaolin Rubber, plastics,
leather substitu¬
ents and fabrics
26214
1 (61)
263 I!Calcination
Magn. sepn.
Flot.
Surface treatment
Bleaching
Removal of iron
impurities
15
16 Experimental research
on beneficiation of kaolin
Whiteness, grain size and abrasive
values suits for the coating material
grade
Hydrocyclone
Horizontal settling
Classification
Magn. sepn.
Bleaching
PaperHGMS 264
17 Beneficiation of kaolin Paper coating 265cn
Mechanical and18 Processing of kaolin CosmeticsNa-hydrosulfite 266
Chemical
methods
Beneficiation of kaolin19 Paper coating 267
Refinement and enrich¬
ment of clay and kaolin
raw materials
Wet sieving
Hydrocyclone
Flot.
Magn. sepn.
Bio-beneficiation
X-ray analysis, x-ray fluoroscence,
DTA, grain size analysis, thermal
dilatometric and SEM
20 Ceramics 268
Beneficiation techniques
and utilization of kaolin
21 Ceramics 269
clay
1 (62)
270A solution of 0.5M H2SO„( 1.0M
H2S03 gas and 20% kaolin were
introduced in neg. and pos.
chambers of efectroly, app.. which
had been provided with a Pt. neg.,
and a graphite pos. electrode resply.
Electrolysis carried out at 0.45A and
acid of 50 mA/cm2 for 1 h.
Iron removal of 61% was achieved.
Porous graphite, Neg. Pt, Al
or stainless steel electrodes,
ElectrolysisBeneficiation techniques
and utilization of kaolin
clays
22
H2S04i H2S03 gas
Calcined at 200-3007h to 900-1200“
for 2-5 h. The pulverised product
contg. 2 20% <24 particles had
brightness 90%
271Refractory
materials
CalcinationRe-examination of
refractory raw materials
23
cncn
Ceramics 272Upgradation of kaolin24
Urea - formaldehyde resin 273Ion-exchangePeculiarities of the
interaction of resins with
kaolinite
25
Disk classifierProduction of dispersed
kaolin
Paper and
chemical
26 274
Industries
CalcinationProperties, processing &
uses of kaolin
27 275
1 (63)
Treated 70% solids of aq.
suspension with 0.3%
Na-hexametaphosphate and NaOH
at pH 6.0. Then treated with a soln.
of Na2S204 dissolved in a 5% soln. of
Na4P207. After 1 h the clay fraction
was pumped at 25 ml/min through a
mixed ion-exchange bed column
{1 part Amberlite IR-120 cation-
exchange resin and 2 parts
Amberlite IR-420 anion-exchange
resin)
276Na-hexametaphosphate,
NaOH, Na2S204, Na4P207lAmberlite IR-120, Amberlite
IR-420
Utilization of polymeric
resin in the processing of
kaolin (removal of iron)
ion-exchange28
cn03
277Paper,
coating
pigments,
extender in
paints, ceramics
plastics and
rubber
Properties and uses of
kaolin
29
30 Thiophene, Piperidine,
Pyridine, Dioxane, THF,
MeOH, EtOH, n-PrOH
Chemisorption Studies were earned out on
montmorillonite, kaolinite and silica
Effect of organic
substances on alumino
silicate adsorbents
278
gel
1 (64)
Exchange of iron, copper
and calcium ions from
clay minerals
Chemisorption Ammonium humates 27931
32 Removal of iron
impurities
The activation energy of the process
is 8-100 KJ/mol.
280Chlorination CO, Cl2
Removal of iron
impurities from kaolin
33 Cyclone size
sepn.
Magn. sepn.
Dithionite
bleaching
281
Prospects of improving
the quality of kaolin
(decreasing the cone, of
CaO and colouring
oxides Fe203 and Ti02)
34 Porcelain and 282
faiencecn-4
Removal of titaniferous
materials from kaolin
Chlorination SOCI2+N35 Kaolin samples were treated with
SOCI2 at 200-500°C and exposed 7h
to flowing N+SOCI2
283
Calcination
Beneficiation of kaolin Dressing36 284,
285
Beneficiation of kaolin
raw materials
Modern37 286tendencies
Processing of kaolin38287
1 (65)
Chemical improvements
of kaolin
Chlorination
Leaching
39 SO?. HCI. NaCI. AlClj, CaCI2& MgClj
The kaolin suspensions were treated
with S02, washing with HCI and iron
ion extraction was promoted by small
amounts of NaCI. AICI3l CaCI; &
MgClj
288
40 Methods of kaolin
investigation
289
Purification, properties
and utilization of kaolin
41 290
minerals
42 Use of coarsely
crystalline potash
feldspar from kaolin
deposits (removal of
iron, titanium and
calcium)
Wet screening Manufacture of 291
electric insulatortnoo
S02, ACOH, H2S04ReductionPurification of clay raw
materials (removing
Fe203 from kaolin)
Clays purified by removing Fe203 by
redn. at pH 4.5, in water, using S02as a reducing agent. ACOH as a
buffer and H2S04 to generate S02from Na2S03. Excess H2S04 was
neutralised by NaOH.
43 292
1 (66)
293The iron and titanium were
transferred to {NH4)2Fe{S04)3(JJ) and
(NH4)2Ti0{S04)2(ll) by (NH4)2S04
treatment at 300°C. Impurities
removed from the kaolin by
dissolving in water contg. an excess
of NH4HS04 and having pH 3 and
£2% H2S04
(NH4)2S04I NH4HS04I
H2SO4
Selec. solubilityRemoval of iron and
titanium minerals from
kaolin raw materials
44
Paper filler 294Poly(Na acrylate),
Na2S204
Upgradation of kaolin
(removal of iron contg.
mica particles)
Froth flot.
Magn. sepn.
Helical centrifuge
45
cnCD
ReductivePossibilities for improv¬
ing the brightness of
kaolin clays
Paper filler 29546
bleaching
Flot.
Magn. sepn.
Selec.
sedimentation
Centrifuge
processing
Kaolin dispersed in water using
Na4P207.7, Calgon. 1, Soda ash
1 Ib/ton and treated in a centrifuge at
1000 rpm for 5 min.
Na4P207l Calgon, Soda ashRemoval of coarse
materials and mineral
impurities from clay
47 2M
1 (67)
297Preparation of enhanced
whiteness of kaolin
products
Calcination48 {NH4)2$04, CO, High temp.
49 The influence of iron and
titanium on the
brightness of kaolins
298
58 g Kaolin, calcined 1 h at 800°,
stirred 3 h at 60° with 1000 ml of
6N HCI, filtered, washing with water,
dried and ground to give 29.8 g of a
white pigment.
50 Whiteness improvement
of Kaolin
6MHCICalcination 299
O)
o
Magn. sepn. :
Selec. floe. :
Selec, disp. :
Seq. sepn. :
Magnetic separation
Selective flocculation
Selective dispersion
Sequential separation
FlotationFlot.
1 (68)
OBJECTIVE:
Calixarenes, a new class of the organic reagents, have recently received
considerable attention by posing amazing applicability in various diversified
The calixarenes with increased selectivity, sensitivity and specificity
towards inorganic ions are competing as excellent analytical reagents. A review
of the literature reveals that not much work has been reported for the extraction
and separation of transition metal ions by using hexasulfonato calix(6)arene
(HSC(6)). In particular no data so far have been reported for the separation and
determination of Fe(III), Mo(VI) and Ti(IV) ions. With this in view it is desirable to
develop the suitable solvent extraction and trace determination of these metalV
ions and their removal from the minerals.
31-39fields.
India is endowed with rich resources of kaolin. The kaolin reserves
located primarily in the states of West Bengal, Rajasthan, Orissa, Kerala,
Meghalaya, Andhra Pradesh, Tamil Nadu, Bihar, Gujarat, Jammu & Kashmir,
Karnataka and Madhya Pradesh.
The recoverable kaolin reserves are estimated to be around 986 million
tonnes (18.9 million tonnes proved, 291.3 million tonnes probable and 675.6
million tonnes of possible) (Fig. 1). The world production of china clay was
placed at about 20.0 million tonnes. Indian production was only 0.66 million
tonnes as against total Indian reserves of about 986 million tonnes. The kaolin
consuming industries differ greatly -in their specific requirements. Statewise
production of the industrial specific kaolinsÿshown in Table-9.
The various techniques which have been applied to date to process Kutch
kaolins are still rather conventional type such as levigation, air flotation, filtration,
need for the upgration of the kaolins by using
new techniques. The calixarenes can be used along with other polymers viz.,
carboxymethyl cellulose (CMC) and polyvinylpyrrolidone (PVP) to improve the
quality of the kaolins.
sun-drying etc. Hence there is a
61
1 (69)
Table - 9
The Recoverable Kaolin Reserves in India
Usable property of kaolin reservesContributing states (Approximate %)Specific Industry Total reserves (Approx.)(thousand crores)
Plasticity, shrinkage after firing and
drying, color after firing and
refractoriness.
Meghalaya (33), Rajasthan (30), Gujarat (17),
Andhra Pradesh (11), West Bengal (6),
Kerala (3.5), Assam (2.5), Haryana (1.6),
Delhi (1.2), Tamil Nadu (0.35),
Maharashtra (0.2), Karnataka (0.25),
Bihar (0.02), Orissa (0.02)
128750Ceramics
O)
NJ
Karnataka (50), Orissa (40), Andhra Pradesh (9),
Bihar (0.05), Maharashtra (0.04).
Filler, reinforcing agent and stiffening
agent.
3410Rubber
Andhra Pradesh (85), Karnataka (14),
Orissa (0.7)
Filling and coating purposes to provide
smooth even surface and imparting
glaze.
980Paper
Karnataka (100)85 Making colored and khadi cloths, used
as sizing and backing agent.
Textile
1 (70)
Andhra Pradesh (77),
Madhya Pradesh (23)
Used as catalysts in improving the yield
of petroleum from crude oils and as a
highly selective molecular sieve
zeolites.
fchemicals 6450
As a distributing agent in disinfectants
like DDT.
Andhra Pradesh (90), Karnataka (8),
Rajasthan (1)
19700Insecticides
Used as an extender or suspending
agent.
Paint
Used for powder, adhesives, surgical
plasters, lotion, ointments, stomach
powders and tablets.
Cosmetics &05CO
Pharmaceuticals
West Bengal (29), Rajasthan (21), Kerala (11),
Tamil Nadu (5), Bihar (4), Jammu and
Kashmir (2.3), Andhra Pradesh (1.6), Madhya
Pradesh (1.5), Karnataka (1.5), Delhi (0.4),
Gujarat (0.35), Pondicherry (0.25),
Maharashtra (0.25), Orissa (0.2), Haryana (0.01),
Assam (0.004), Goa (0.001), Uttar Pradesh
(0.001).
826650Unclassified/ Not
known
1 (71)
V9
fOroono Ol o01 o
1I1 i
fvTl
(Q Andhra Pradesh (5.2)
Assam (0.32)73CD
\)no Bihar (3.5)<<D
CSD3Delhi (0.5)tr
CD f »
*7T ©Gao (0.0015)D) OO o
oO3 oGujarat (2.5) o
CDoW3CD Haryana (0.2)5 OU>CD
MIW
Jammu & Kashmir (2.0)3
3Karnataka (1.1)a
Ml
w
Kerala (9.5)
m Madhya Pradesh (1.5)
L Maharastra (0.3)
Meghalaya (5.3J
f*\ £ MU Orissa (16.0)
Pondichary (0.24)
Rajasthan (21.0)if;
Tamilnadu (4.5)
h Uttar Pradesh (0.0012)
- vv :
' V ** -yt
West Bengal (25.0)
1 (72)
PRESENT INVESTIGATION:
Organic reagents play a vital role in inorganic separations and
analyses. A large number of the reagents have been reported, however, still
there is a need for new types of reagents for the separation and
determination of metal ions. Calixarenes are a new class of the compounds
which have remarkable versatility for complexation with several metal ions.
However, not much work ha& been reported for the extraction of transition
metals. Hence in the present investigation a hexasulfonated calix(6)arene
has been synthesized and used for the separation and determination of
metals. It is also envisaged to remove the trace impurities of the metals from
the kaolin to improve its quality.
The thesis describes the 'synthesis of hexasulfonated calix(6)arene
(HSC(6)) and its characterisation with m.p., IR, NMR and Mass spectra.
The rapid sensitive, selective extraction and spectrophotometric
methods have been developed for the determination of iron, molybdenum
and titanium using HSC(6), These metals can be estimated in the presence
of several diverse ions. The extract was directly injected to the plasma
for ICP-AES measurements which increases the sensitivity by several folds.
The developed methods are applied for the determination of iron,
molybdenum and titanium in high purity alloys and kaolin samples.
A new selective flocculation separation (SFS) scheme has been
developed for the trace removal of discolouring metal impurities viz., titanium
and iron from the kaolin clay matrix. The SFS scheme comprises the use of
polyvinyl pyrrolidone (PVP) as dispersant, carboxymethyl cellulose (CMC)
enriching agent. The results were confirmed through pH studies, chemical
analysis and brightness studies.
as
65
1 (73)
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